CN110433802A - A kind of hydrogenation catalyst and preparation method thereof and the catalyst are used for the method that alpha, beta-unsaturated aldehyde adds hydrogen to prepare saturated aldehyde - Google Patents
A kind of hydrogenation catalyst and preparation method thereof and the catalyst are used for the method that alpha, beta-unsaturated aldehyde adds hydrogen to prepare saturated aldehyde Download PDFInfo
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
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Abstract
The present invention discloses a kind of hydrogenation catalyst and preparation method thereof and the catalyst is used for the method that alpha, beta-unsaturated aldehyde adds hydrogen to prepare saturated aldehyde.The active component of the catalyst includes palladium oxide and auxiliary agent, and the auxiliary agent includes one of ruthenium sesquioxide, manganese oxide, rhenium heptoxide, antimony oxide, bismuth oxide and selenium dioxide or a variety of.The catalyst is suitable for alpha, beta-unsaturated aldehyde selective hydrogenation and prepares saturated aldehyde, is particularly suitable for isooctene aldehyde selective hydrogenation and prepares different new aldehyde.Can high conversion, highly selective acquisition target product, this catalyst will be for realizing plus the industrialization for preparing isooctyl acid of hydroxide method has important meaning.
Description
Technical field
The present invention relates to Field of Fine Chemicals, and in particular to a kind of α, beta-unsaturated aldehyde add hydrogen to prepare saturated aldehyde, especially
It is that isooctene aldehyde adds hydrogen to prepare catalyst of different new aldehyde and preparation method thereof and process for selective hydrogenation.
Background technique
Isooctyl acid and its esters are important fine chemicals, are mainly used as all kinds of unsaturated polyester resin promotors and urge
Agent, coating and ink drier, polyvinyl chloride processing aid, intermetallic composite coating and lubricating auxiliary agent, oil dope, the vulcanization of rubber
Promotor can synthesize medicine, dyestuff, pesticide and fragrance etc. additionally as intermediate.There are nearly ten isooctyl acid production enterprises in China
Industry, annual production capacity are about 1.5 ten thousand tons/year, and wherein Shenyang Zhangming Chemical Co., Ltd is the manufacturing enterprise of largest domestic, Nian Sheng
About 6000 tons/year of production capacity power, positive plan enlarging to ten thousand tons/year of scales；Other scopes of the enterprise are smaller, and mostly hundreds of tons/year, simultaneously
Due to home products unstable quality, inferior quality also needs 10000 tons of import or so every year.
Isooctyl acid industry is combined to mainly have two lines, first is that isooctanol oxidizing process, this method using isooctanol as raw material,
It the use of sodium hydroxide and potassium permanganate is that oxidant is aoxidized, the method for reusing sulfuric acid neutralization obtains different pungent by separation
Acid.The method raw material sources reliable operation is simple, but process flow is long, is not easy large-scale production, and all process units in China are equal
It is produced using the route, the problems such as it is low that there are comprehensive yields, and acid-bearing wastewater discharge amount is big, and product quality is poor；Second is that being with butyraldehyde
Raw material is dehydrated by condensation and generates isooctene aldehyde (2- ethyl hexenal), and repeated hydrogenation obtains 2- ethyl hexanal, then aoxidizes
To isooctyl acid, the route raw material is from the horse's mouth, and oxidation of aldehydes method is serialization, and totally-enclosed technique is easy to large-scale production, Europe
The some big companies of U.S. mostly use the route to produce, and the technique is environmentally protective, high income, product quality is high, is appropriate for advising greatly
The industrialized production of mould, but the technique has higher requirement for device quality, catalyst etc. simultaneously, this is also domestic
Never realize industrialized reason.This patent is then to be directed in the technique isooctene aldehyde selective hydrogenation system of core the most
The catalyst and technique of standby different octanal carry out the scientific achievement of many years tackling key problem, for realizing the update of domestic isooctyl acid preparation process
Regenerating has very great meaning.
Domestic many enterprises and scientific research institutions have carried out research to the preparation process of isooctyl acid, such as CN106278875A public affairs
Then the preparation process for having opened a kind of isooctyl acid is used using isooctanol and highly basic in 180~290 DEG C of 1.5~16h of reaction of temperature
Up to thick isooctyl acid after sour acidification reaction object, isooctyl acid is made in purified handle；Isooctyl acid is prepared in this way, and utilization is non-
Sulfuric acid carries out acidification and replaces sulfuric acid in the prior art, and the by-product species of acquisition are abundant, has a wide range of application, and added value is high.
The patent using it is a kind of substitute sulfuric acid acid neutralized, but unavoidable yield it is low and generate acid-bearing wastewater the case where；
CN104945238A discloses a kind of method for preparing isooctyl acid, which is raw material using octanol, by sodium hydroxide high temperature
Reaction, adds cobalt iso-octoate as catalyst, reacts a few hours at 250 DEG C, finally make to neutralize with sulfuric acid to obtain isooctyl acid,
The patent uses cobalt iso-octoate as oxidation catalyst, but contains there are still pyroreaction, using highly basic sodium hydroxide, generation
The problems such as sour waste water；The country adds the research of hydrogen more for octenal, but most octenals that surround thoroughly add hydrogen to prepare octanol
Technique expansion, such as CN104549304A disclose a kind of catalyst and preparation method thereof of gas phase hydrogenation of octenal to octanol.It should
The waste catalyst that direct method production methylchlorosilane generates is crushed, sieves by method, by roasting, acid dissolution, urea hydrothermal deposition
Step obtains the catalyst of the gas phase hydrogenation of octenal to octanol to its modifying and decorating, and ingredient contains copper, zinc active component
With porous oxidation silicon carrier.The advantages of patent, is: solving the high level of solid residue waste catalyst in organosilicon compound probability
Change problem of complex utilization, low raw-material cost, operating method are simple.Catalyst activity described in this patent is higher, by octenal
Direct hydrogenation is octanol, can not be highly selective prepare different octanal；A kind of CN104119204A discloses octenal plus hydrogen side
Method.That patent describes the technique for using 2% Pd/C (5%) catalyst to add hydrogen to prepare octanol octenal, the patent advantages
Can effectively to carry out adding hydrogen to double bond, and catalyst can be recycled using palladium catalyst.The same patent uses
Octenal has also directly been hydrogenated into octanol by palladium catalyst, can not be highly selective only the double bond of isooctene aldehyde is carried out plus hydrogen,
High yield prepares different octanal；CN105080549A discloses a kind of catalyst for preparing 2-ethylhexanol by gas-sphase hydrogenation of octylene aldehyde and its system
Preparation Method.It proposes a kind of highly selective octene aldehyde hydrogenating catalyst using distribution precipitating preparation, while solving catalyst and existing
The problem of dusting is easy to appear in use process, catalyst are mainly organized as copper oxide 25~35%, zinc oxide 45~60%, oxygen
Change aluminium 2~10%, silica 2~10%, auxiliary agent 0.01~1%, the patent is by optimizing traditional copper system hydrogenation catalyst
Formula obtained preferable effect.The patent only addresses only the pulverizing problem of catalyst in octenal hydrogenation process, and
Directly add hydrogen to octanol octenal.
In summary patent, the patent that the country prepares different octanal about isooctene aldehyde selective hydrogenation at present are less.It is different pungent
The Major Difficulties of olefine aldehydr selective hydrogenation are that the hydrogenation activity of one, carbon-carbon double bond and aldehyde radical is very close, for catalyst
Activity have a higher requirement, activity is too high, will lead to and is thoroughly hydrogenated to octanol；Activity is too low, will lead to raw material conversion
Rate is low, and since isooctene aldehyde stability is poor, it is relatively low to eventually lead to yield；Secondly, due to isooctene aldehyde in reaction process, different pungent
The side reaction that aldehyde, isooctyl acid etc. can intersect mutually, side reaction are mainly to be condensed and polymerize the high waste formed, these are high
Waste exists in the form of tar, can attach in catalyst surface, to influence the property of catalyst, therefore preparation can effectively inhibit
The catalyst that side reaction occurs is particularly important.
In the technique that isooctene aldehyde adds hydrogen to prepare different new aldehyde, the selectivity of catalyst how is improved, improves hydrogenation catalyst
The stability of agent and service life are this field urgent problems to be solved.
Summary of the invention
The present invention provides a kind of hydrogenation catalyst and preparation method thereof, and the catalyst is suitable for α, beta-unsaturated aldehyde selection
Property hydrogenation reaction prepares saturated aldehyde, is particularly suitable for isooctene aldehyde selective hydrogenation and prepares different new aldehyde.With very good effect
Fruit has the prospect of industrial use.
In order to solve the above technical problems, the present invention the following technical schemes are provided:
A kind of α, beta-unsaturated aldehyde add hydrogen to prepare the catalyst of saturated aldehyde, including carrier and active component, the active group
Dividing includes palladium oxide and auxiliary agent, and the auxiliary agent includes ruthenium sesquioxide, manganese oxide, rhenium heptoxide, antimony oxide, three oxidations
One of two bismuths and selenium dioxide are a variety of.
As a preferred embodiment, auxiliary agent of the present invention includes consisting of: ruthenium sesquioxide, manganese oxide
With at least one of rhenium heptoxide and at least one of antimony oxide and bismuth oxide.
As another preferred embodiment, auxiliary agent of the present invention includes consisting of: ruthenium sesquioxide, oxidation
At least one of manganese and rhenium heptoxide, at least one of antimony oxide and bismuth oxide and selenium dioxide.
Carrier of the present invention includes one of activated carbon, silica and aluminum oxide or a variety of.
Catalyst of the present invention, including consisting of:
0.05~1wt% of palladium oxide, preferably 0.1~0.8wt%, more preferable 0.3~0.5wt%；
0.001~0.1wt% of ruthenium sesquioxide, preferably 0.005~0.08wt%, more preferable 0.03~0.05wt%；
Manganese oxide and/or rhenium heptoxide 0.001~0.1wt%, preferably 0.005~0.08wt%, more preferable 0.03~
0.05wt%；
Antimony oxide and/or bismuth oxide 0.001~0.01wt%, preferably 0.002~0.008wt%, more preferably
0.003-0.006；
Selenium dioxide 0-0.01wt%, preferably 0.001-0.01wt%, more preferable 0.005-0.008wt%；
98.9~99.90wt% of carrier, preferably 99.15-99.85wt%, more preferable 99.40-99.60wt%.
A method of preparing catalyst of the present invention, comprising the following steps: proportionally,
(1) it will be added in palladium salt aqueous solution and impregnate in carrier, it is dry；
(2) step (1) products therefrom is added to containing in ruthenium salt, manganese salt, perrhenic acid, antimonic salt, bismuth salt and selenium oxide
It is impregnated in one or more solution, it is dry；
(3) step (2) products therefrom is roasted.
Carrier of the present invention is pre-processed before the use, and the pretreated step is included in 400~600
DEG C roasting 2~4 hours.
In step (1) of the present invention, the temperature of dipping is 10~25 DEG C, and the time of dipping is 4~24 hours, preferably 12
~18 hours.
In step (2) of the present invention, the temperature of dipping is 10~25 DEG C, and the time of dipping is 4~24 hours, preferably 12
~18 hours.
In the solution of step (2) of the present invention, the concentration of the palladium salt is 0.001~1.0g/L, preferably 0.02~
0.8g/L。
In the solution of step (2) of the present invention, the concentration of the ruthenium salt is 0.001~1.0g/L, preferably 0.01~
0.5g/L。
In the solution of step (2) of the present invention, the concentration of the manganese salt or perrhenic acid is 0.001~1.0g/L, preferably
0.01~0.5g/L.
In the solution of step (2) of the present invention, the concentration of the antimonic salt or bismuth salt is 0.001-0.5g/L, preferably
0.01-0.3g/L。
In step (2) of the present invention, selenium dioxide is added directly into solution and is prepared, due to selenium oxide have compared with
Good water solubility, therefore the mixed solution of stable homogeneous can be formed under stiring, selenium oxide will form fine in reduction process
Selenides, to ensure that the extension of catalyst service life.
Palladium salt of the present invention, ruthenium salt, manganese salt, antimonic salt, bismuth salt can be selected from the salt of respective element well known in the art,
Such as nitrate, halide, sulfate, carbonate, it is preferred that palladium salt is palladium nitrate, and ruthenium salt is nitric acid ruthenium, and manganese salt is manganese nitrate,
Antimonic salt includes but is not limited to one of nitric acid antimony, antimony sulfate, antimony trichloride, carbonic acid antimony or a variety of, and bismuth salt includes but is not limited to
One of bismuth nitrate, bismuth sulfate, bismuth trichloride, waltherite are a variety of.
In step (3) of the present invention, the temperature of roasting is 400~700 DEG C, preferably 550~650 DEG C, the time of roasting
It is 2~8 hours, preferably 4~6 hours.
Catalyst of the present invention just has corresponding catalytic activity after being restored.Preferred restoring method packet
It includes following steps: being restored by way of heating up in proper order, heating rate is 0.1~10 DEG C/min, final reduction temperature
It is 200~500 DEG C, reducing gas is the gaseous mixture of hydrogen and inert gas, the preferred nitrogen of gaseous mixture, hydrogen in gaseous mixture
Volume content be 0.1~25v%.
Catalyst of the present invention is suitable for alpha, beta-unsaturated aldehyde selective hydrogenation and prepares saturated aldehyde, such as following formula institute
Show:
Wherein R1And R2Mutually independent expression alkyl or H, the alkyl include methyl, ethyl, propyl, isopropyl, tertiary fourth
Base.
Catalyst of the present invention is particularly suitable for isooctene aldehyde selective hydrogenation and prepares different octanal, isooctene aldehyde
Hydrogenation reaction formula is as follows:
The condition of selective hydrogenation of the present invention includes: that reactor is fixed bed reactors, and reaction temperature is
50~200 DEG C, preferably 80~120 DEG C, more preferable 90~110 DEG C；Reaction pressure be 0.5~5MPa of gauge pressure, preferably 1~3MPa,
More preferable 1.5~2.5MPa；The molar ratio of hydrogen and α, beta-unsaturated aldehyde are 1~10:1, preferably 2~8:1, more preferable 3~5:
1；Raw material alpha, beta-unsaturated aldehyde Feed space velocities are 0.001~1h-1, preferably 0.01~0.5h-1, more preferable 0.1~0.25h-1。
Ruthenium element outermost layer s electronics and time outer layer d electronics can participate in bonding, can be formed with ruthenium sesquioxide, therefore can
It gives the enough electronics transfer spaces of the intermediate product formed in reaction process and forms protection；And rhenium and manganese element are for catalysis
The stability of agent provides help；Antimony and bismuth then uniformly and in terms of water-resistance have the Elemental redistribution during shaping of catalyst
Good effect (isooctene aldehyde raw material contains a small amount of water, and catalyst needs certain water-resistance)；The addition of selenium element is also
The hydrogen selenide formed during former can make selenides of many precipitation by metallic ion as particle, this ensure that amount of activated gold
Belong to the chemical valence of element still in metal ion state, and as hydrogenation catalyst uses the extension of time, gradually carries out part
Reduction, to be conducive to the service life and activity holding of catalyst.Therefore the catalyst is greatly improved isooctene aldehyde and adds hydrogen
The selectivity and yield of different octanal are prepared, has and realizes industrialized prospect.
The positive effect of the present invention is: the preparation method of this catalyst is simple, and catalyst dispersity is good, with higher
Industrial prospect.Using the catalyst and technique, isooctene aldehyde conversion ratio is greater than 99.9%, and different octanal is selectively greater than 98%,
Catalyst still keeps preferable activity, and catalyst itself is stable, does not occur catalyst after verifying in life test 1000 hours
The case where broken and dusting.
Specific embodiment
Hydrogenation liquid gas phase analysis method:
Analysis instrument: Agilent 7820A, capillary column (J&W 122-5532:3569.41079
DB-5ms, 325 DEG C: 30m × 320m × 0.5 μm)
Gas phase analysis method: area normalization method
Gas phase analysis condition: 250 DEG C of injection port heater, pressure 11.724psi, overall flow rate 32.366mL/min, dottle pin
Purge flow rate 1.3661mL/min, split ratio 30:1, bypass flow 30mL/min；Column temperature is temperature programming: initial temperature 60
DEG C, keep 1min；80 DEG C are risen to the rate of 10 DEG C/min, 1min is kept, then rises to 250 DEG C with the rate of 15 DEG C/min,
Keep 8min, runing time 23.333 minutes.Detector is fid detector, 260 DEG C of heater, carrier gas: high-purity N2；Air stream
Measure 400mL/min, hydrogen flowing quantity 30mL/min, make-up gas flow 25mL/min, 0.2 μ L of sample volume.
Catalyst 1
By γ-Al2O30.19 gram of palladium nitrate is added to 1000 millis before use, first at 450 DEG C roast 4h by carrier
It rises in deionized water, the γ-Al of 100 grams of above-mentioned processing is added2O312h is impregnated after being sufficiently stirred at room temperature, dry 4 at 120 DEG C
Hour, by the product of drying and 0.0012 gram of selenium dioxide, 0.076 gram of nitric acid ruthenium, 0.0025 gram of manganese nitrate, 0.0021 gram of nitre
It is impregnated 24 hours in sour 1000 ml deionized water of antimony, is dried 5 hours in 100 DEG C, above-mentioned solid is subjected to roasting 4 at 550 DEG C
Hour, obtaining group becomes palladium oxide 0.1wt%, ruthenium sesquioxide 0.03wt%, manganese oxide 0.001wt%, antimony oxide
0.001wt%, the oxidized catalyst of selenium dioxide 0.001wt%, 99.867wt% carrier alundum；Pre- use should
Catalyst needs are restored by way of heating up in proper order, and heating rate is 0.3 DEG C/min, and final reduction temperature is 500
DEG C, the content of hydrogen is 0.3v% in reducing gas, remaining is nitrogen, until bed temperature gradually rises hydrogen after stablizing 24 hours
Content until hydrogen content is stablized in tail gas, obtains catalyst 1 to 25v%.
Catalyst 2
By γ-Al2O30.56 gram of palladium nitrate is added to 1000 millis before use, first at 450 DEG C roast 4h by carrier
It rises in deionized water, the γ-Al of 100 grams of above-mentioned processing is added2O312h is impregnated after being sufficiently stirred at room temperature, dry 4 at 110 DEG C
Hour, by the product of drying, be added to containing: 0.0025 gram of nitric acid ruthenium, 0.10 gram of manganese nitrate, 0.0034 gram of bismuth nitrate 1000
It impregnates 24 hours in milliliter aqueous solution, is dried in 110 DEG C, above-mentioned solid is carried out to roasting 4 hours at 600 DEG C, obtaining group becomes
Palladium oxide 0.3wt%, ruthenium sesquioxide 0.001wt%, manganese oxide 0.04wt%, bismuth oxide 0.002wt%,
The oxidized catalyst of 99.657wt% carrier alundum；In advance using the catalyst need by way of heating up in proper order into
Row reduction, heating rate are 0.3 DEG C/min, and final reduction temperature is 500 DEG C, and the content of hydrogen is in reducing gas
0.3v%, remaining is nitrogen, until bed temperature gradually rises hydrogen content to 25v% after stablizing 24 hours, hydrogen contains in tail gas
Until amount is stablized, catalyst 2 is obtained.
Catalyst 3
By γ-Al2O30.93 gram of palladium nitrate is added to 1000 millis before use, first at 450 DEG C roast 4h by carrier
It rises in deionized water, the γ-Al of 100 grams of above-mentioned processing is added2O312h is impregnated after being sufficiently stirred at room temperature, dry 4 at 120 DEG C
Hour, by the product of drying and 0.0024 gram of selenium dioxide, 0.076 gram of nitric acid ruthenium, 0.0025 gram of manganese nitrate, 0.0021 gram of nitre
Sour antimony, which is added in 1000 ml deionized waters, to be impregnated 24 hours, in 100 DEG C dry 5 hours, by above-mentioned solid 550 DEG C into
Row roasting 4 hours, obtaining group becomes palladium oxide 0.5wt%, ruthenium sesquioxide 0.03wt%, manganese oxide 0.001wt%, three oxidations
Two antimony 0.001wt%, the oxidized catalyst of selenium dioxide 0.002wt%, 99.466wt% carrier alundum；Make in advance
It needs to be restored by way of heating up in proper order with the catalyst, heating rate is 0.3 DEG C/min, and final reduction temperature is
500 DEG C, the content of hydrogen is 0.3v% in reducing gas, remaining is nitrogen, until bed temperature gradually rises after stablizing 24 hours
Hydrogen content until hydrogen content is stablized in tail gas, obtains catalyst 3 to 25v%.
Catalyst 4
By γ-Al2O30.93 gram of palladium nitrate is added to 1000 millis before use, first at 450 DEG C roast 4h by carrier
It rises in deionized water, the γ-Al of 100 grams of above-mentioned processing is added2O312h is impregnated after being sufficiently stirred at room temperature, dry 5 at 100 DEG C
Hour, by the product of drying be added to containing 0.00301 gram of selenium dioxide, 0.1013 gram of nitric acid ruthenium, 0.0105 gram of nitric acid antimony,
It impregnates 24 hours, is dried 5 hours in 110 DEG C, by above-mentioned solid 600 in 1000 milliliters of aqueous solutions of 0.0415 gram of perrhenic acid
Roasting 4 hours DEG C is carried out, obtaining group becomes palladium oxide content 0.5wt%, ruthenium sesquioxide 0.04wt%, rhenium heptoxide
0.04wt%, antimony oxide 0.005wt%, the oxidized catalyst of selenium dioxide 0.003wt%, 99.412wt% carrier；
It needs to be restored by way of heating up in proper order using the catalyst in advance, heating rate is 0.3 DEG C/min, final reduction temperature
Degree be 500 DEG C, in reducing gas the content of hydrogen be 0.3v%, remaining is nitrogen, until bed temperature stablize 24 hours after gradually
Hydrogen content is increased to 25v%, until hydrogen content is stablized in tail gas, obtains catalyst 4.
Catalyst 5
By γ-Al2O30.74 gram of palladium nitrate is added to 1000 millis before use, first at 450 DEG C roast 4h by carrier
It rises in deionized water, the γ-Al of 100 grams of above-mentioned processing is added2O312h is impregnated after being sufficiently stirred at room temperature, dry 5 at 100 DEG C
Hour, by the product of drying be added to containing 0.00401 gram of selenium dioxide, 0.081 gram of nitric acid ruthenium, 0.0068 gram of bismuth nitrate,
It is impregnated 24 hours in 1000 milliliters of aqueous solutions of 0.00104 gram of perrhenic acid, is dried 5 hours in 110 DEG C, above-mentioned solid is existed
600 DEG C carry out roasting 4 hours, and obtaining group becomes palladium oxide content 0.4wt%, ruthenium sesquioxide 0.03wt%, rhenium heptoxide
0.001wt%, bismuth oxide 0.004wt%, selenium dioxide 0.004wt%, 99.561wt% are that the oxidation state of carrier is catalyzed
Agent；It needs to be restored by way of heating up in proper order using the catalyst in advance, heating rate is 0.3 DEG C/min, and final goes back
Former temperature is 500 DEG C, and the content of hydrogen is 0.3v% in reducing gas, remaining is nitrogen, until after bed temperature stablizes 24 hours
Hydrogen content is gradually risen to 25v%, until hydrogen content is stablized in tail gas, obtains catalyst 5.
Catalyst 6
By γ-Al2O30.75 gram of palladium nitrate is added to 1000 millis before use, first at 450 DEG C roast 4h by carrier
It rises in deionized water, the γ-Al of 100 grams of above-mentioned processing is added2O312h is impregnated after being sufficiently stirred at room temperature, dry 5 at 100 DEG C
Hour, by the product of drying be added to containing 0.00501 gram of selenium dioxide, 0.081 gram of nitric acid ruthenium, 0.0126 gram of nitric acid antimony,
It impregnates 24 hours, is dried 5 hours in 110 DEG C, by above-mentioned solid 600 in 1000 milliliters of aqueous solutions of 0.036 gram of perrhenic acid
Roasting 4 hours DEG C is carried out, oxidation palladium content 0.4wt%, ruthenium sesquioxide 0.03wt%, rhenium heptoxide are obtained
0.035wt%, antimony oxide 0.006wt%, selenium dioxide 0.005wt%, 99.524wt% are that the oxidation state of carrier is catalyzed
Agent needs to be restored by way of heating up in proper order using the catalyst in advance, and heating rate is 0.3 DEG C/min, and final goes back
Former temperature is 500 DEG C, and the content of hydrogen is 0.3v% in reducing gas, remaining is nitrogen, until after bed temperature stablizes 24 hours
Hydrogen content is gradually risen to 25v%, until hydrogen content is stablized in tail gas, obtains catalyst 6.
Catalyst 7
By γ-Al2O30.75 gram of palladium nitrate is added to 1000 millis before use, first at 450 DEG C roast 4h by carrier
It rises in deionized water, the γ-Al of 100 grams of above-mentioned processing is added2O312h is impregnated after being sufficiently stirred at room temperature, dry 5 at 100 DEG C
Hour, by the product of drying be added to containing 0.0070 gram of selenium dioxide, 0.108 gram of nitric acid ruthenium, 0.0136 gram of bismuth nitrate,
It impregnates 24 hours, is dried 5 hours in 110 DEG C, by above-mentioned solid 600 in 1000 milliliters of aqueous solutions of 0.046 gram of perrhenic acid
Roasting 4 hours DEG C is carried out, oxidation palladium content 0.4wt%, ruthenium sesquioxide 0.04wt%, rhenium heptoxide are obtained
0.045wt%, bismuth oxide 0.008wt%, selenium dioxide 0.007wt%, 99.50wt% are that the oxidation state of carrier is catalyzed
Agent needs to be restored by way of heating up in proper order using the catalyst in advance, and heating rate is 0.3 DEG C/min, and final goes back
Former temperature is 500 DEG C, and the content of hydrogen is 0.3v% in reducing gas, remaining is nitrogen, until after bed temperature stablizes 24 hours
Hydrogen content is gradually risen to 25v%, until hydrogen content is stablized in tail gas, obtains catalyst 7.
Catalyst 8
By γ-Al2O30.83 gram of palladium nitrate is added to 1000 millis before use, first at 450 DEG C roast 4h by carrier
It rises in deionized water, the γ-Al of 100 grams of above-mentioned processing is added2O312h is impregnated after being sufficiently stirred at room temperature, dry 5 at 100 DEG C
Hour, the product of drying is added to containing 0.0081 gram of selenium dioxide, 0.0168 gram of nitric acid antimony, 0.041 gram of perrhenic acid
1000 milliliters of aqueous solutions in impregnate 24 hours, dried 5 hours in 110 DEG C, above-mentioned solid carried out at 600 DEG C to roasting 4 hours,
Obtain oxidation palladium content 0.45wt%, rhenium heptoxide 0.04wt%, antimony oxide 0.008wt%, selenium dioxide
0.008wt%, 99.494wt% are the oxidized catalyst of carrier, are needed by way of heating up in proper order using the catalyst in advance
It is restored, heating rate is 0.3 DEG C/min, and final reduction temperature is 500 DEG C, and the content of hydrogen is in reducing gas
0.3v%, remaining is nitrogen, until bed temperature gradually rises hydrogen content to 25v% after stablizing 24 hours, hydrogen contains in tail gas
Until amount is stablized, catalyst 8 is obtained.
Catalyst 10
By γ-Al2O30.75 gram of palladium nitrate is added to 1000 millis before use, first at 450 DEG C roast 4h by carrier
It rises in deionized water, the γ-Al of 100 grams of above-mentioned processing is added2O312h is impregnated after being sufficiently stirred at room temperature, dry 5 at 100 DEG C
Hour, the product of drying is added to containing 0.005 gram of selenium dioxide, 0.108 gram of nitric acid ruthenium, 0.088 gram of manganese nitrate
It impregnates 24 hours in 1000 milliliters of aqueous solutions, is dried 5 hours in 110 DEG C, above-mentioned solid is carried out to roasting 4 hours at 600 DEG C, is obtained
To oxidation palladium content 0.40wt%, ruthenium sesquioxide 0.04wt%, manganese oxide 0.035wt%, selenium dioxide 0.005wt%,
99.52wt% is the oxidized catalyst of carrier, needs to be restored by way of heating up in proper order using the catalyst in advance, is risen
Warm rate is 0.3 DEG C/min, and final reduction temperature is 500 DEG C, and the content of hydrogen is 0.3v% in reducing gas, remaining is nitrogen
Gas until hydrogen content is stablized in tail gas, obtains until bed temperature gradually rises hydrogen content to 25v% after stablizing 24 hours
Catalyst 10.
Catalyst 11
By γ-Al2O30.84 gram of palladium nitrate is added to 1000 millis before use, first at 450 DEG C roast 4h by carrier
It rises in deionized water, the γ-Al of 100 grams of above-mentioned processing is added2O312h is impregnated after being sufficiently stirred at room temperature, dry 5 at 100 DEG C
Hour, the product of drying is added to containing 0.0041 gram of selenium dioxide, 0.108 gram of nitric acid ruthenium, 0.031 gram of perrhenic acid
It impregnates 24 hours in 1000 milliliters of aqueous solutions, is dried 5 hours in 110 DEG C, above-mentioned solid is carried out to roasting 4 hours at 600 DEG C, is obtained
To oxidation palladium content 0.45wt%, ruthenium sesquioxide 0.04wt%, rhenium heptoxide 0.03wt%, selenium dioxide
0.004wt%, 99.476wt% are the oxidized catalyst of carrier, are needed by way of heating up in proper order using the catalyst in advance
It is restored, heating rate is 0.3 DEG C/min, and final reduction temperature is 500 DEG C, and the content of hydrogen is in reducing gas
0.3v%, remaining is nitrogen, until bed temperature gradually rises hydrogen content to 25v% after stablizing 24 hours, hydrogen contains in tail gas
Until amount is stablized, catalyst 11 is obtained.
Catalyst 12
By γ-Al2O30.65 gram of palladium nitrate is added to 1000 millis before use, first at 450 DEG C roast 4h by carrier
It rises in deionized water, the γ-Al of 100 grams of above-mentioned processing is added2O312h is impregnated after being sufficiently stirred at room temperature, dry 5 at 100 DEG C
Hour, the product of drying is added to containing 0.0036 gram of selenium dioxide, 0.108 gram of nitric acid ruthenium, 0.0105 gram of nitric acid antimony
It impregnates 24 hours in 1000 milliliters of aqueous solutions, is dried 5 hours in 110 DEG C, above-mentioned solid is carried out to roasting 4 hours at 600 DEG C, is obtained
To oxidation palladium content 0.35wt%, ruthenium sesquioxide 0.04wt%, antimony oxide 0.05wt%, selenium dioxide
0.0035wt%, 99.556wt% are the oxidized catalyst of carrier, need the side by heating up in proper order using the catalyst in advance
Formula is restored, and heating rate is 0.3 DEG C/min, and final reduction temperature is 500 DEG C, and the content of hydrogen is in reducing gas
0.3v%, remaining is nitrogen, until bed temperature gradually rises hydrogen content to 25v% after stablizing 24 hours, hydrogen contains in tail gas
Until amount is stablized, catalyst 12 is obtained.
Catalyst 13
By γ-Al2O30.75 gram of palladium nitrate is added to 1000 millis before use, first at 450 DEG C roast 4h by carrier
It rises in deionized water, the γ-Al of 100 grams of above-mentioned processing is added2O312h is impregnated after being sufficiently stirred at room temperature, dry 5 at 100 DEG C
Hour, the product of drying is added to containing 0.0041 gram of selenium dioxide, 0.108 gram of nitric acid ruthenium, 0.0085 gram of bismuth nitrate
It impregnates 24 hours in 1000 milliliters of aqueous solutions, is dried 5 hours in 110 DEG C, above-mentioned solid is carried out to roasting 4 hours at 600 DEG C, is obtained
To oxidation palladium content 0.40wt%, ruthenium sesquioxide 0.04wt%, bismuth oxide 0.005wt%, selenium dioxide
0.004wt%, 99.551wt% are the oxidized catalyst of carrier, are needed by way of heating up in proper order using the catalyst in advance
It is restored, heating rate is 0.3 DEG C/min, and final reduction temperature is 500 DEG C, and the content of hydrogen is in reducing gas
0.3v%, remaining is nitrogen, until bed temperature gradually rises hydrogen content to 25v% after stablizing 24 hours, hydrogen contains in tail gas
Until amount is stablized, catalyst 13 is obtained.
Catalyst 14
By γ-Al2O30.75 gram of palladium nitrate is added to 1000 millis before use, first at 450 DEG C roast 4h by carrier
It rises in deionized water, the γ-Al of 100 grams of above-mentioned processing is added2O312h is impregnated after being sufficiently stirred at room temperature, dry 5 at 100 DEG C
Hour, by the product of drying be added to containing 0.00401 gram of selenium dioxide, 0.081 gram of nitric acid ruthenium, 0.057 gram of manganese nitrate,
It impregnates 24 hours, is dried 5 hours in 110 DEG C, by above-mentioned solid 600 in 1000 milliliters of aqueous solutions of 0.0082 gram of nitric acid antimony
Roasting 4 hours DEG C is carried out, oxidation palladium content 0.40wt%, ruthenium sesquioxide 0.03wt%, manganese oxide 0.03wt%, three oxygen are obtained
Change two antimony 0.004wt%, selenium dioxide 0.004wt%, 99.532wt% are the oxidized catalyst of carrier, are urged in advance using this
Agent needs are restored by way of heating up in proper order, and heating rate is 0.3 DEG C/min, and final reduction temperature is 500 DEG C,
The content of hydrogen is 0.3v% in reducing gas, remaining is nitrogen, is contained until bed temperature gradually rises hydrogen after stablizing 24 hours
Amount until hydrogen content is stablized in tail gas, obtains catalyst 14 to 25v%.
Catalyst 9
By γ-Al2O30.85 gram of palladium nitrate is added to 1000 millis before use, first at 450 DEG C roast 4h by carrier
It rises in deionized water, the γ-Al of 100 grams of above-mentioned processing is added2O3Carrier impregnates 16h after being sufficiently stirred at room temperature, at 100 DEG C
It is 5 hours dry, above-mentioned solid is carried out to roasting 4 hours at 600 DEG C, aoxidizes palladium content 0.45wt%, 99.55%wt carrier.It rises
Warm rate is 0.3 DEG C/min, and final reduction temperature is 500 DEG C, and the content of hydrogen is 0.3v% in reducing gas, remaining is nitrogen
Gas until hydrogen content is stablized in tail gas, obtains until bed temperature gradually rises hydrogen content to 25v% after stablizing 24 hours
Catalyst 9.
Comparative example 1
Catalyst filling 9 in fixed bed reactors, catalyst loading are 100 milliliters, gauge pressure 2.5MPa, temperature 105
DEG C, feedstock air speed is 0.14h-1, hydrogen aldehyde molar ratio 3.5, feed stock conversion 99.5%, different octanal selectivity 85% is different
For octanol selectivity 13% or so, remaining is polymerization high boiling point product.
Embodiment 2
Catalyst filling 1 in fixed bed reactors, catalyst loading are 100 milliliters, reaction pressure 1.6MPa,
90 DEG C of temperature, feedstock air speed is 0.16h-1, hydrogen aldehyde molar ratio 3, feed stock conversion 99.6%, different octanal selectivity
94.3%, isooctanol selectivity 3%, remaining is polymerization high boiling point product.
Embodiment 3
Catalyst filling 2 in fixed bed reactors, catalyst loading are 100 milliliters, reaction pressure 2.0MPa,
95 DEG C of temperature, feedstock air speed is 0.18h-1, hydrogen aldehyde molar ratio 4, feed stock conversion 99.5%, different octanal selectivity
93.5%, isooctanol selectivity 4.7%, remaining is polymerization high boiling point product.
Embodiment 4
Catalyst filling 3 in fixed bed reactors, wherein catalyst loading is 100 milliliters, and reaction pressure is
2.0MPa, 105 DEG C of temperature, feedstock air speed is 0.20h-1, hydrogen aldehyde molar ratio 2.5, feed stock conversion 99.6% is different pungent
Aldehyde selectivity 95.6%, isooctanol selectivity 2.6%, remaining is polymerization high boiling point product.
Embodiment 5
Catalyst filling 4 in fixed bed reactors, catalyst loading are 100 milliliters, reaction pressure 2.3MPa,
95 DEG C of temperature, feedstock air speed is 0.19h-1, hydrogen aldehyde molar ratio 5, feed stock conversion 99.8%, different octanal selectivity
97.4%, for isooctanol selectivity 1.7%, remaining is polymerization high boiling point product.
Embodiment 6
Catalyst filling 5 in fixed bed reactors, catalyst loading are 100 milliliters, reaction pressure 1.5MPa,
90 DEG C of temperature, feedstock air speed is 0.16h-1, hydrogen aldehyde molar ratio 3, feed stock conversion 99.7%, different octanal selectivity
96.7%, for isooctanol selectivity 1.8%, remaining is polymerization high boiling point product.
Embodiment 7
Catalyst filling 6 in fixed bed reactors, catalyst loading are 100 milliliters, reaction pressure 2.3MPa,
100 DEG C of temperature, feedstock air speed is 0.20h-1, hydrogen aldehyde molar ratio 4.5, feed stock conversion 99.6%, different octanal selectivity
97.8%, for isooctanol selectivity 1.3%, remaining is polymerization high boiling point product.
Embodiment 8
Catalyst filling 7 in fixed bed reactors, catalyst loading are 100 milliliters, reaction pressure 1.7MPa,
85 DEG C of temperature, feedstock air speed is 0.23h-1, hydrogen aldehyde molar ratio 4.7, feed stock conversion 99.6%, different octanal selectivity
97.8%, for isooctanol selectivity 1.7%, remaining is polymerization high boiling point product.
Embodiment 9
Catalyst filling 8 in fixed bed reactors, catalyst loading are 100 milliliters, reaction pressure 3MPa, temperature
108 DEG C, feedstock air speed is 0.21h-1, hydrogen aldehyde molar ratio 3.5, feed stock conversion 99.2%, different octanal selectivity
94.9%, for isooctanol selectivity 2.1%, remaining is polymerization high boiling point product.
Embodiment 10
Catalyst filling 10 in fixed bed reactors, catalyst loading are 100 milliliters, reaction pressure 4MPa, temperature
105 DEG C of degree, feedstock air speed are 0.21h-1, hydrogen aldehyde molar ratio 3.0, feed stock conversion 99.4%, different octanal selectivity
93.9%, for isooctanol selectivity 3.2%, remaining is polymerization high boiling point product.
Embodiment 11
Catalyst filling 11 in fixed bed reactors, catalyst loading are 100 milliliters, reaction pressure 4MPa, temperature
105 DEG C of degree, feedstock air speed are 0.25h-1, hydrogen aldehyde molar ratio 5.0, feed stock conversion 99.1%, different octanal selectivity
94.1%, for isooctanol selectivity 4.3%, remaining is polymerization high boiling point product.
Embodiment 12
Catalyst filling 12 in fixed bed reactors, catalyst loading are 100 milliliters, reaction pressure 5MPa, temperature
115 DEG C of degree, feedstock air speed are 0.25h-1, hydrogen aldehyde molar ratio 5.0, feed stock conversion 99.3%, different octanal selectivity
93.7%, for isooctanol selectivity 4.1%, remaining is polymerization high boiling point product.
Embodiment 13
Catalyst filling 13 in fixed bed reactors, catalyst loading are 100 milliliters, reaction pressure 2.5MPa,
100 DEG C of temperature, feedstock air speed is 0.20h-1, hydrogen aldehyde molar ratio 4.0, feed stock conversion 99.4%, different octanal selectivity
92.5%, for isooctanol selectivity 4.5%, remaining is polymerization high boiling point product.
Embodiment 14
Catalyst filling 14 in fixed bed reactors, catalyst loading are 100 milliliters, reaction pressure 3.7MPa,
107 DEG C of temperature, feedstock air speed is 0.24h-1, hydrogen aldehyde molar ratio 3.5, feed stock conversion 99.2%, different octanal selectivity
91.9%, for isooctanol selectivity 3.9%, remaining is polymerization high boiling point product.
Embodiment 15:
Catalyst filling 7 in fixed bed reactors, catalyst loading are 100 milliliters, reaction pressure 2.5MPa,
95 DEG C of temperature, feedstock air speed is 0.20h-1, hydrogen aldehyde molar ratio 4.0 has carried out 2000 hours life assessments, small 2000
When evaluation in, feed stock conversion is between 98.5-99.5, and different new aldehyde selectivity is 96% or so, and wherein isooctanol selectivity exists
1.5% or so, catalyst is activity stabilized in evaluation in 2000 hours.
Claims (10)
1. a kind of α, beta-unsaturated aldehyde adds hydrogen to prepare the catalyst of saturated aldehyde, including carrier and active component, the active component
Including palladium oxide and auxiliary agent, the auxiliary agent includes ruthenium sesquioxide, manganese oxide, rhenium heptoxide, antimony oxide, three oxidations two
One of bismuth and selenium dioxide are a variety of.
2. catalyst according to claim 1, which is characterized in that the auxiliary agent includes consisting of: ruthenium sesquioxide, oxygen
Change at least one of manganese and rhenium heptoxide and at least one of antimony oxide and bismuth oxide；It is furthermore preferred that
The auxiliary agent includes consisting of: ruthenium sesquioxide, at least one of manganese oxide and rhenium heptoxide, antimony oxide and three
Aoxidize at least one of two bismuths and selenium dioxide.
3. catalyst according to claim 1 or 2, which is characterized in that the catalyst, including consisting of:
0.05~1wt% of palladium oxide, preferably 0.1~0.8wt%, more preferable 0.3~0.5wt%；
0.001~0.1wt% of ruthenium sesquioxide, preferably 0.005~0.08wt%, more preferable 0.03~0.05wt%；
Manganese oxide and/or rhenium heptoxide 0.001~0.1wt%, preferably 0.005~0.08wt%, more preferable 0.03~
0.05wt%；
Antimony oxide and/or bismuth oxide 0.001~0.01wt%, preferably 0.002~0.008wt%, more preferably
0.003-0.006；
Selenium dioxide 0-0.01wt%, preferably 0.001-0.01wt%, more preferable 0.005-0.008wt%；
98.9~99.90wt% of carrier, preferably 99.15-99.85wt%, more preferable 99.40-99.60wt%.
4. catalyst according to claim 1-3, which is characterized in that the carrier includes activated carbon, titanium dioxide
One of silicon and aluminum oxide are a variety of.
5. a kind of method for preparing the described in any item catalyst of claim 1-4, comprising the following steps: proportionally,
(1) it will be added in palladium salt aqueous solution and impregnate in carrier, it is dry；
(2) step (1) products therefrom is added to containing one of ruthenium salt, manganese salt, perrhenic acid, antimonic salt, bismuth salt and selenium oxide
Or impregnated in a variety of solution, it is dry；
(3) step (2) products therefrom is roasted.
6. described pre- according to the method described in claim 5, it is characterized in that, the carrier is pre-processed before the use
The step of processing, is included in 400~600 DEG C and roasts 2~4 hours.
7. method according to claim 5 or 6, which is characterized in that in the step (3), the temperature of roasting is 400~
700 DEG C, preferably 550~650 DEG C, the time of roasting are 2~8 hours, preferably 4~6 hours.
8. a kind of α, the method that beta-unsaturated aldehyde hydrogenation reaction prepares saturated aldehyde, which is characterized in that the hydrogenation reaction is in right
It is required that under the catalysis of the described in any item catalyst of 1-4 or the catalyst of the described in any item method preparations of claim 5-7
It carries out, the chemical formula of the α, beta-unsaturated aldehyde areThe chemical formula of the saturated aldehyde isWherein R1And R2Mutually independent expression alkyl or H, the alkyl are selected from methyl, ethyl, third
Base, isopropyl, tert-butyl.
9. according to the method described in claim 8, it is characterized in that, the α, beta-unsaturated aldehyde are isooctene aldehyde.
10. method according to claim 8 or claim 9, which is characterized in that the condition of the hydrogenation reaction includes: reaction temperature
It is 50~200 DEG C, preferably 80~120 DEG C, more preferable 90~110 DEG C；Reaction pressure be 0.5~5MPa of gauge pressure, preferably 1~
3MPa, more preferable 1.5~2.5MPa；Hydrogen and α, the molar ratio of beta-unsaturated aldehyde are 1~10:1, preferably 2~8:1, more preferable 3
~5:1；Alpha, beta-unsaturated aldehyde Feed space velocities are 0.001~1h-1, preferably 0.01~0.5h-1, more preferable 0.1~0.25h-1。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114558572A (en) * | 2022-03-10 | 2022-05-31 | 万华化学集团股份有限公司 | Hydrogenation catalyst, preparation method thereof and method for preparing citronellol |
| CN115814820A (en) * | 2022-12-19 | 2023-03-21 | 山东中科新材料研究院有限公司 | Hydrogenation catalyst, preparation method thereof and preparation method of N, N-dimethylcyclohexylamine |
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| CN116041159A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Method for preparing isooctyl aldehyde |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1102796A (en) * | 1964-03-07 | 1968-02-07 | Wacker Chemie Gmbh | Process for the manufacture of saturated aliphatic aldehydes |
| GB1310143A (en) * | 1969-08-16 | 1973-03-14 | Basf Ag | Manufacture of 2-ethylhexanal-1 |
| JPS5748938A (en) * | 1980-09-05 | 1982-03-20 | Japan Synthetic Rubber Co Ltd | Preparation of carboxylic acid ester |
| CN1466486A (en) * | 2000-09-29 | 2004-01-07 | �й�ʯ�ͻ����ɷ�����˾ | Unsaturated hydrocarbon selective hydrogenation catalyst, its preparation process and use thereof |
| CN101687181A (en) * | 2007-05-10 | 2010-03-31 | 巴斯夫欧洲公司 | Method for producing amines |
| CN102188969A (en) * | 2010-03-16 | 2011-09-21 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst of cracked gasoline and preparation method of selective hydrogenation catalyst |
| CN103007929A (en) * | 2012-12-07 | 2013-04-03 | 上海华谊（集团）公司 | Pd-based catalyst prepared through colloid deposition, preparation method and application |
| CN103157491A (en) * | 2011-12-12 | 2013-06-19 | 中国科学院生态环境研究中心 | Mesoporous metal oxide-supported palladium catalyst used for catalytic oxidation of volatile organic compounds |
| CN106925267A (en) * | 2017-03-01 | 2017-07-07 | 武汉凯迪工程技术研究总院有限公司 | The catalytic evaluation method of selective hydrocatalyst and preparation method and its generation isobutylaldehyde |
| US20170217866A1 (en) * | 2016-01-28 | 2017-08-03 | Eastman Chemical Company | Single-step conversion of n-butyraldehyde to 2-ethylhexanal |
| CN107876047A (en) * | 2017-11-19 | 2018-04-06 | 西安凯立新材料股份有限公司 | A kind of preparation method of α, β unsaturated aldehyde/ketone hydrogenation Pd/C catalyst |
-
2018
- 2018-05-04 CN CN201810417176.5A patent/CN110433802B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1102796A (en) * | 1964-03-07 | 1968-02-07 | Wacker Chemie Gmbh | Process for the manufacture of saturated aliphatic aldehydes |
| GB1310143A (en) * | 1969-08-16 | 1973-03-14 | Basf Ag | Manufacture of 2-ethylhexanal-1 |
| JPS5748938A (en) * | 1980-09-05 | 1982-03-20 | Japan Synthetic Rubber Co Ltd | Preparation of carboxylic acid ester |
| CN1466486A (en) * | 2000-09-29 | 2004-01-07 | �й�ʯ�ͻ����ɷ�����˾ | Unsaturated hydrocarbon selective hydrogenation catalyst, its preparation process and use thereof |
| CN101687181A (en) * | 2007-05-10 | 2010-03-31 | 巴斯夫欧洲公司 | Method for producing amines |
| CN102188969A (en) * | 2010-03-16 | 2011-09-21 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst of cracked gasoline and preparation method of selective hydrogenation catalyst |
| CN103157491A (en) * | 2011-12-12 | 2013-06-19 | 中国科学院生态环境研究中心 | Mesoporous metal oxide-supported palladium catalyst used for catalytic oxidation of volatile organic compounds |
| CN103007929A (en) * | 2012-12-07 | 2013-04-03 | 上海华谊（集团）公司 | Pd-based catalyst prepared through colloid deposition, preparation method and application |
| US20170217866A1 (en) * | 2016-01-28 | 2017-08-03 | Eastman Chemical Company | Single-step conversion of n-butyraldehyde to 2-ethylhexanal |
| CN106925267A (en) * | 2017-03-01 | 2017-07-07 | 武汉凯迪工程技术研究总院有限公司 | The catalytic evaluation method of selective hydrocatalyst and preparation method and its generation isobutylaldehyde |
| CN107876047A (en) * | 2017-11-19 | 2018-04-06 | 西安凯立新材料股份有限公司 | A kind of preparation method of α, β unsaturated aldehyde/ketone hydrogenation Pd/C catalyst |
Non-Patent Citations (4)
| Title |
|---|
| YAN LI ET AL.: "Effect of transition metals (Cr, Mn, Fe, Co, Ni and Cu) on selective hydrogenation of cinnamaldehyde over Pt/CNTs catalyst", 《REACTION KINETICS AND CATALYSIS LETTERS》 * |
| 布鲁克斯，B.T.等: "《石油烃化学 第3卷 第1分册》", 31 August 1963, 中国工业出版社 * |
| 李杰等: "α,β-不饱和醛/酮中C＝C双键选择性加氢催化剂的研究进展", 《工业催化》 * |
| 汪多仁著: "《精细化工中间体》", 31 January 2008, 海洋出版社 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116041159A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Method for preparing isooctyl aldehyde |
| CN114558572A (en) * | 2022-03-10 | 2022-05-31 | 万华化学集团股份有限公司 | Hydrogenation catalyst, preparation method thereof and method for preparing citronellol |
| CN114558572B (en) * | 2022-03-10 | 2023-12-19 | 万华化学集团股份有限公司 | Hydrogenation catalyst, preparation method thereof and method for preparing citronellol |
| CN115814820A (en) * | 2022-12-19 | 2023-03-21 | 山东中科新材料研究院有限公司 | Hydrogenation catalyst, preparation method thereof and preparation method of N, N-dimethylcyclohexylamine |
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| CN115814820B (en) * | 2022-12-19 | 2024-03-22 | 山东中科新材料研究院有限公司 | Hydrogenation catalyst, preparation method thereof and preparation method of N, N-dimethylcyclohexylamine |
| CN115845881B (en) * | 2022-12-19 | 2024-04-26 | 山东中科新材料研究院有限公司 | Hydrogenation catalyst and preparation method thereof, and preparation method of N, N-dimethylbenzylamine |
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